Halogenated aryl mono-ethers of 9, 10-dihydroxystearic acid and salts thereof



2,942,913 were J di 960 necessary 'to use excess alkali, if an alkali metal salt is 2,942,013 9,10-epoxystearic acid is employed.

HALOGEN ATED MONGETHERS F 9,104! The products in the form of their salts or as the free 'HYDROXYSTEARIC ACID AND SALTS THERE acids are outstandingly useful as agricultural poisons, in CF 7 particular as herbicides. In the form of their water soluble salts, they are eifective germicidal soaps and emulsifying agents. Their polyvalent metal soaps (lead, zinc, barium, aluminum, calcium, etc.) are useful as addi-. tives for lubricating oils for improving lubricity. The 10 copper and mercury salts are useful fungicides and bactericides.

The following examples illustrate processes carried out in accordance with the invention.

Herman A. Bruson, North Haven, and Jack Rofckett,

New Haven, Coma, assignors toOlin Mathieson Chemical Corporation, New Haven, Gonna, a corporation of Virginia 7 c No Drawing. Filed June 10, 1955, Ser. No. 514,689

4 Claims. (Cl. 260-408) This invention relates to organic. compounds and their production, and has for its object. the provision of halo genated aryl mono-ethers of 9,10-dihydroxystearic acid and salts thereof, and a process of producing the cornand PeIItaChIOIQPhBIIOI- -6 5) i 350 of y Y I uene was stirred and boiled under reflux for five hours.

The process the invention cgmprises reacting halo- The 1101116116 \VaS then Ofi at reduced pressure genated phenols in the presence of an alkaline catalyst mIIly) T e W Phase System became with a salt of 9,10-epoxystearic acid to form a salt of homogeneous durmg T1115 dlslllna'flmi- Water 9 halogenated mono-aryl ether of 9,10-dihydroxystearic concentrated hydrochloric afiid. Was T acid. The process includes acidification of the salts thus f P 2 the reaction mixture Was Subjected 10 Steam fo d m f the cal-boxylic acids and the Subsequent distillation to remove smallamounts of excess pentaconversion th r of to Salts. chlorophenol. The residual oil was separated, taken up The process of the invention yields a n'rixtureoftwoin ether and washed to pH 6.0. The ether was then isomers hi are hydroxy compounds di t9 h removed by evaporation. The product was a viscous Example 1 A mixture of dry sodium 9,10-epoxystearate (80.1 g.)

erties of which correspond to a material consisting eswherein R is -a halogenated aryl radical and M is a metal;

sentially of Upon acidification, a mixture of the two carboxylic acids corresponding to (a) and (b) above is obtained, oHi)1oH-.oH- c11, g00H M being, replaced by hydrogen. 7 I 40 The new compounds in accordance with invention B may accordingly be defined as 9,10. disubstituted stearic C] 01 acids, one substituent being hydroxyl and the other sub- 7 stituent being a halogenated aryloxy; and include Salts C1 C1 of such disubstituted stearic acids. The compounds CI may berepresented by the formula:

CHa((JH2)r C]?[-:-Q1 *(CEQJTQQQM and onuomn-on-ongcmhooon I I H wherein A represents hydrogen or 'ahalqgenated aryl, B is hydrogen when A is a halogenated and and a halo- G1 genated aryl when A is hydrogen, -and M is a monovalent radical chosen from the group consisting of liy- Cl 01 drogen, a metal, ammonium and substituted ammonium Q1 radicals, and the saturated organic radical of an alcohol. Among the halogenated phenols which can be used in the process of the invention for forming the new A mixture of Sodium L g), para chlorpheno1 compounds are the tetra and P (32.1 g.) and 150 cc. of toluene was stirred and heated p n l as w as the corresponding fluoww under reflux until all the sodium had dissolved. Then brome, or iodophenols- The phenols used can contain 92.3 g. of dry sodium 9,10-epoxystearate was added with other nuclear substituents besides halogen such as, for 200 cc. of additional toluene. example, alkyl, aryl, aralkyl, cycloalkyl, alkoxy and aryl- The mixture was stirred and boiled under reflux for oxy groups. 4 hours, after which the toluene was distilled off under The reaction is preferably carried out in the presence reduced pressure. Water plus 45 cc. of concentrated of an alkaline catalyst such as the alkali metals, their hydrochloric acid was added and the mixture was steam oxides, alcoholates, hydrides, amides and hydroxides distilled. When no more chlorophenol came over, the which areefiicient for the purpose, notably sodium and residual oil was separated, taken up in ether, washed, sodium hydroxide. When the phenol is strongly acidic dried, filtered and evaporated to dryness. as in the case of tetraand pentachlorophenol, it is not The residual product was a clear yellow oil weighing Example 2 and cmwmn-cn-omonnmoorr Ex'amples and 4 V In the same manner as in Example 2, 2,4-dichlorophenol and 2,4,5-trichlorophenol react with sodium 9,10- epoxystearate to yield respectively 2,4-dichlorophenoxyhydroxystearic acid and 2,4,5-trichlorophenoxy hydroxystearic acid. as pale yellow thick oils. v

Example 5 A mixture of 38.1 g. of para-bromophenol, 150cc. of toluene and 0.9 g. of sodium was stirred and boiled under reflux until all the sodium had dissolved. The solution became deep red. Then 74 g. of dry sodium 9,10-epoxystearate was added and 200 cc. more of toluene.

Br and 4 The 7 sodium 9,10-ep0xystearate used in the above specific examples was a commercial product containing 86.7% of the epoxystearate, the balance consisting mainly of stearate and some dihydroxystearate having no adverse effect on the syntheses? The starting material may be of higherorlower purity, the reacting propor: itions being in each case selected in accordance with the content of active reagent.

The halogenated aryl mono-ethers of 9,10-dihydroxystearic acid produced in accordance with the above specific examples are viscous pale yellow oils having a density greater than that of water.

" cablefor use as weed killers.

. The mixture was stirred and boiled 4 hours under In accordance with the above process, p-iodophenol and p-fluorophenbl react with sodium 9,10-epoxystearate to yield, respectively, p-iodophenoxy-hydroxystearic acid and p-fluorophenoxy-hydroxystearic acid as pale yellow thick oils.

When the product is desired in the form of an alkali metal salt, it may be recovered as such from the reaction mixture or by neutralizing the free acid with the alkali metal oxide or hydroxide. Other salts, as of the alkaline earth metals and other polyvalent metals may be prepared by double decomposition reactions between an alkali metal (particularly lithium, sodium or potassium) saltof the halogenated aryl mono-ether of 9,10-dihydroxylstearic acid and a soluble salt of the other metal. In many cases, the polyvalent metal salts can also be made by neutralizing the free acid with the metal oxide or hydroxide. i a

The halogenated aryl mono-ethers of 9,1Q-dihydroxystearic acid and salts thereof, as described above, possess herbicidal properties and are advantageously appli- The water-soluble salts, particularly the sodium, potassium, ammonium and substituted ammonium salts are .useful as germicidal soaps and emulsifying agents. The polyvalent metal salts,

* such as those of calcium, lead, zinc, barium and aluminum,- may be'added to lubricating oils and greases for enhancing the lubricity and other desirable properties. -The copper :and mercury salts are effective fungicides and bactericides. r

.We claim: 5'1. A compound of the group consisting of a halogenated-aryl mono-ether of 9,10-dihydroxystearic acid and inorganic saltsthereof. p 2. Pentachlorophenyl mono-ether of 9,10-dihydroxy stearicacid. g

3. Para-chloropheriy'l mono-ether of 9,10-dihydroxystearic acid.

4. Para-bromophenyl mono-ether of 9,10-dihydroxystearic acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,s42,os2 swam Feb. 20, 1951 

1. A COMPOUND OF THE GROUP CONSISTING OF A HALOGENATED-ARYL MONO-ETHER OF 9,10-DIHYDROXYSTEARIC ACID AND INORGANIC SALTS THEREOF. 